Molybdenum-containing lubricant compositions



United States Patent O 3,541,014 MOLYBDENUM-CONTAINING LUBRICANTCOMPOSITIONS William M. Le Suer, Cleveland, Ohio, assignor to TheLubrizol Corporation, Wicklilfe, Ohio, a corporation of Ohio N Drawing.Filed July 12, 1967, Ser. No. 652,671 The portion of the term of thepatent subsequent to Feb. 17, 1987, has been disclaimed Int. Cl. Cm1/10, 1/32 US. Cl. 25249.7 Claims ABSTRACT OF THE DISCLOSURE Thedisclosure sets forth lubricant compositions having improved extremepressure capabilities and anti-wear properties which are characterizedby the presence therein of oil-soluble molybdenum-containing organiccomplexes. These complexes are produced by contactingmolybdenumcontaining anions with oil-soluble overbased, Group II metalcontaining compositions until a portion of the anions react with GroupII rnetal. Lubricating oils, cutting oils, greases, and the like areillustrative of the lubricant compositions disclosed.

This invention relates to improved lubricating compositions.Particularly, the invention relates to lubricating compositions havingimproved extreme pressure (ER) and antiwear capabilities.

As is well known, many present day lubricating problems involveproviding adequate lubrication between moving metal surfaces which arebrought into a forceful working relationship. Thus, there is a need forlubricants of sufficient lubricity to provide lubrication between thehearing surfaces of moving metal components where the bear ing surfacesare subjected to large forces at the point of contact. These forces andthe accompanying friction result in the generation of heat whichelevates the metal temperatures. If the pressure is sufficiently highand the relative motion between surfaces suflicient, very high metaltemperatures can result. Thus, in extreme cases, the contacting metalsurfaces may actually weld. With less extremes of pressure, theinadequate lubrication between the surfaces is manifested in acceleratedwear, scoring, scuffing, etc.

The lubricating compositions of the invention possess improved extremepressure and antiwear capabilities and are particularly useful in anenvironment where such properties are necessary or desirable.Lubricating compositions used in such environments include cutting oils,hypoid gear oils, metal drawing compounds, turbine oils, motor oils,automatic transmission fluids, and metal-forming lubricants.

Many diverse additives for enhancing El. and antiwear properties areknown in the prior art. Examples of such additives are chlorinated wax,alkyl polysulfides, alkyl phosphites, alkaryl phosphates, metaldithiophosphates, sulfurized sperm oil, sulfurized olefins, and thelike. However, the prior art does not disclose molybdenum-containingcomplexes of the type utilized in the present lubricating compositionsto be effective E.P. and anti-wear additives.

In accordance with the foregoing, it is a principal object of thisinvention to provide improved lubricating compositions.

A further object of the invention is to provide lubricant compositionshaving extreme pressure and anti-wear capabilities.

Another object is to provide lubricant compositions characterized by thepresence therein of novel molybdenum-containing complexes.

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Another object of the invention is to provide a method for impartingextreme pressure properties and anti-wear properties to the lubricantcompositions by incorporating into such compositionsmolybdenum-containing complexes.

These and other objects of the invention are accomplished by providing alubricating composition characterized by the presence of a major amountof a lubricant such as a lubricating oil or a lubricating grease and aminor amount of an oil-soluble molybdenum-containing complex of theempirical formula R M A E In this formula, R represents an equivalent ofan organic oleophilic group, M represents an equivalent of a Group IImetal, A represents an equivalent of the anion of an inorganic acid, Eis an equivalent of a molybdenum-containing anion. The superscripts x,n, y, and z represent the number of equivalents of R, -M, A, and E,respectively, present in the complez. The ratio of nzx is at least 2:1,It is at least 2, x and z are each at least 1, and n=x+y+z With theproviso that [y can be zero.

The molybdenum-containing complexes corresponding to the above-indicatedformula are prepared by contacting a solution of overbased, Group IIImetal-containing organic complex with molybdenum-containing anions untilat least a portion of the molybdenum-containing anions react with GroupII metal. Generally, the solution of the overbased organic complex iscontacted with a solution containing molybdate anions. As explained inmore detail hereinafter, the formation of the molybdenum-containingcomplex is facilitated by conducting the process in the presence ofpeptizing agents.

The overbased, Group II metal-containing intermediates are a well-knownclass of basic metal-containing compositions which have generally beenemployed as detergents and dispersants in lubricating oil compositions.These overbased intermediates are also referred to in the art assuperbased or hyperbased complexes or salts, basic complexes, basicmetal complexes, high-metal containing salts and complexes, basiccomplex salts, and the like.

Overbased materials are characterized by a metal content in excess ofthat which would be present according to the stoichiometry of the metal"and the particular organic compound said to be overbased. Thus, if anoil-soluble monosulfonic acid,

is neutralized with a basic metal compound, e.g., calcium hydroxide thenormal metal salt produced will contain one equivalent of calcium foreach equivalent of acid, i.e.,

However, various known procedures are available which produceoil-soluble products containing more than the stoichiometric amount ofmetal. These oil-soluble products are the overbased materials employedas intermediates to prepare the molybdenum-containing complexesincorporated in the lubricating compositions of the invention.

Applying these known procedures, an oil-soluble sulfonic acid or analkali or alkaline earth metal salt thereof can be reacted with a GroupII metal base and the product will contain an amount of metal in excessof that required to neutralize the acid, for example, 4.5 times as muchmetal as present in the normal salt, or a metal excess of 3.5equivalents. The actual stoichiometric excess of metal can varyconsiderably, for example, from about 0.1 equivalent to about 30 or moreequivalents depending on the reactions, the process conditions, and thelike. These overbased products useful in preparing themolybdenum-containing complexes will contain at least about 2.0 to about30 or more equivalents of Group II metal for each equivalent of thematerial which is overbased.

In the present specification and claims the term overbased is used todesignate materials containing a stoichiometric excess of metal and is,therefore, inclusive of those materials which have been referred to inthe art as overbased, superbased, hyperbased, etc., as discussed supra.

The terminology metal ratio is used in the prior art and herein todesignate the ratio of the total chemical equivalents of the metal inthe overbased product to the chemical equivalents of the metal in theproduct which would be expected to result in the reaction between theorganic material to be overbased and the Group II metal base accordingto the known chemical reactivity and stoichiometry of the two reactants.Thus, in the normal calcium sulfonate discussed above, the metal ratiois one and in the overbased sulfonate, the metal ratio is 4.5.

Generally, these overbased materials are prepared by treating a reactionmixture comprising (a) the organic compound to be overbased, (b) areaction medium consisting essentiallyof at least one substantiallyinert, organic solvent for said organic material, (c) a stoichio metricexcess of a metal base, and (d) a promoter with an acidic material. Themethods for preparing the overbased products and an extremely diversegroup of overbased products are well known in the prior art and aredisclosed, for example, in the following U.S. patents:

2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925;2,617,049; 2,695,910; 2,723,234; 2,723,235; 2,723,236; 2,760,970;2,767,164; 2,767,209; 2,777,874; 2,798,852; 2,839,470; 2,856,359;2,856,360; 2,856,361; 2,861,951; 2,883,340; 2,915,517; 2,959,551;2,968,642; 2,971,014; 2,989,463; 3,001,981; 3,027,325; 3,070,581;3,108,960; 3,147,232; 3,133,019; 3,146,201; 3,152,991; 3,155,616;3,170,880; 3,170,881; 3,172,855; 3,194,823; 3,223,630; 3,232,883;3,242,079; 3,242,080; 3,250,710; 3,256,186; 3,274,135; and 3,312,618.These patents disclose typical overbased products useful in preparingmolybdenum-containing complexes and are incorporated herein by referencefor their discussion of the processes and materials suitable forpreparing such products.

The alkaline earth metal overbased products are preferred for use asstarting materials in preparing the molybdenum-containing complexes.Barium overbased products are especially desirable due to the ease withwhich they are converted to the molybdenum-containing complexes and theexcellent results achieved.

Organic compounds which can be overbased are generally oil-solublecompounds characterized by an essentially hydrocarbon portion containingat least about 12 aliphatic carbon atoms or at least about 8 aliphaticcarbon atoms and one or more aromatic hydrocarbon rings and a polarportion such as an acid group. The hydrocarbon portion may contain polarsubstituents so long as the hydrophilic character thereof is notdestroyed. The hydrocarbon portion may contain up to 250 or more carbonatoms but generally will contain not more than about 60 carbon atoms.Organic compounds particularly suitable for overbasing are described inmore detail below.

Suitable acids include oil-soluble organic acids such as phosphorusacids, thiophosphorus acids, sulfur acids, carboxylic acids,thiocarboxylic acids, and the like, as well as the corresponding alkaliand alkaline earth metal salts thereof. Patents 2,616,904; 2,695,910;2,767,- 164; 2,767,209; 2,777,874; 3,147,232; and 3,274,135 disclose avariety of overbased products which can be prepared from diverse organicacid starting materials. Overbased acids wherein the acid is aphosphorus acid, a thiophosphorus acid, phosphorus acid-sulfur acid com-4 bination, or sulfur acid prepared from polyolefins are disclosed in2,883,340; 2,915,517; 3,001,981; 3,108,960; and 3,232,883. Overbasedphenates are disclosed in 2,959,- 551 while overbased ketones are foundin 2,798,852.

A variety of overbased products prepared from oilsoluble metal-free,non-tautomeric neutral and basic organic polar compounds such as esters,amines, amides, alcohols, ethers, sulfides, sulfoxides, and the like aredisclosed, for example in 2,968,642; 2,971,014; and 2,989,463.

The esters are preferably esters of fatty acids having from about 12 toabout 30 carbon atoms in the acyl moiety while the alcoholic moiety canbe derived from and alcohol of up to 30 carbon atoms. Exemplary alcoholsinclude methanol, ethanol, propanol, sorbitol, pentaerythritol, allylalchol, dodecanol, cyclohexanol and the like. illustrative estersinclude methyl stearate, cyclohexyl oleate, soritol mono-oleate, butylstearate, cyclohexyl oleate, sorbitol mono-oleate, butyl stearate, ethyllaurate, allyl myristrate, ethyl palmitatc, diester of ethylene glycolwith stearic acid, tetraester of pentaerythritol with oleic acid. Of theesters, the commercially supplied fatty acid and esters are particularlyuseful because of their availability and cost. Examples of thesecommercially available products are sperm oil, tall oil, methyl ester oftall oil, and the behenyl ester of tall oil.

Alcohols useful in overbased products are exemplified by dodecylalcohol, octadecyl alcohol, sperm alcohol (obtained by the hydrolysis ofsperm oil), behenyl alcohol, oleyl alcohol, and 0x0 alcohols such as areobtained by the reaction of an olefin having at least 12 carbon atomswith carbon monoxide and hydrogen. They are generally aliphatic alcoholsand may contain up to about 30 aliphatic carbon atoms.

Illustrative of the sulfoxides suitable for preparing overbased productsare the dialiphatic hydrocarbon sulfoxides of up to about 50 aliphaticcarbon atoms such as dodecyl methyl sulfoxide, didodecyl sulfoxide,hexyl octadecyl sulfoxide, dibehenyl sulfoxide, and dioctadecylsulfoxide. The aliphatic groups each normally will contain up to about30 aliphatic carbon atoms and the sulfoxide will have a total of atleast about 12 aliphatic carbon atoms.

Overbased products can be prepared from primary, secondary, or tertiaryaliphatic amines containing at least about 12 aliphatic carbon atoms.Exemplary amines include, for example, dodecylamine, didodecylamine, N-methyl dodecylamine, N-benzyl octadecylamine, dicyclohexylamine,tridecylamine, N- butyl laurylamine, and N,N-dimethyl pentadecylamine.They also include polyamines such as N-octadecyl propylenediamine,N-decylpropylenediamine, tridecyl-substituted diethylenetriamine andoctyl-substituted tetraethylenepentamine. The preferred polyamines areN-alkyl-su'bstituted alkylenepolyamines such as the N-alkyl substitutedethylenediamines, trimethylenediamines, tetramethylenediamines,triethylenetetramines, and pentaethylenehexamines. The polyamines maycontain one or more N-alkyl substituents. The alkyl group of suchN-alkyl-substituted polyamines can contain from about 8 to 40 or morecarbon atoms but preferably will have from about 12 to about 30 carbonatoms. Other polyamines having an acyl substituent such as characterizesimidazolines, on one or more of the amino groups are also useful. Theyare illustrated by the reaction product of one mole of oleic acid withone mole of triethylenetetramine. Still other amines useful herein maybe hydroxyalkyl amines, including hydroxyalkyl polyamines, in which thehydroxy alkyl radical has up to about 30 carbon atoms. Normally thehydroxyalkyl group has upto about 6 carbon atoms. Such hydroxyalkylamines are formed by the reaction of an epoxide such as ethylene oxide,propylene oxide, or epichlorohydrin with dodecyl amine, N-octadecyltrimethylenediamine, or didecylamine.

Condensation products of the above-identified amines with a loweraliphatic aldehyde, i.e., one having less than about six carbon atoms,constitute a preferred class of overbased products suitable asintermediates in synthesizing the molybdenum complexes. Examples of thealdehydes preferred for use herein are formaldehyde (or formaldehydeproducing compositions such as paraformaldehyde or aqueous formalin),acetaldehyde, propionaldehyde, butyraldehyde, and the like. Thecondensation products are readily obtained by mixing one mole of theamine with from about 0.5 to about moles of the aldehyde and thenheating the mixture at a temperature from about 50 C. to 240 C. orhigher. Where the amine or the aldehyde is a solid, the condensation isbest carried out in the presence of a diluent such as mineral oil,xylene, benzene, naphtha, chlorobenzene or other substantially inertsolvent. The condensation is promoted by the presence in the reactionmixture of a small amount, at least about 0.01% and usually less than byweight of the aldehyde, of a basic catalyst such as an alkali metalhydroxide or an alkaline earth metal hydroxide, e.g., sodium hydroxide,potassium hydroxide, calcium hydroxide, or barium hydroxide. The precisenature of the condensation products is not known. The condensationproducts prepared from a mixture of from 2 to 4 moles of formaldehyde ora formaldehyde producing compound and about one mole of an N-alkylalkylenediamine in which the alkyl radical has from about 10 to 30carbon atoms and the alkylene radical has from 2 to 4 carbon atoms areespecially useful in preparing overbased products suitable asintermediates in the preparation of the molybdenum-containing complexes.Barium overbased amine-aldehyde condensation products are preferred.

Another class of materials which can be overbased are the oil-soluble,nitro-substituted aliphatic hydrocarbons, particularly nitro-substitutedpolyolefins such as polyethylene, polypropylene, polyisobutylene, etc.Materials of this type are illustrated in 2,959,551.

The metal compounds used in preparing the overbased products arenormally the basic salts of metals in Group II of the Periodic Table.The anionic portion of the salt can be hydroxyl, oxide, carbonate,hydrogen carbonate, nitrate, sulfite, hydrogen sulfite, halide, amide,sulfate, etc. as disclosed in the above-cited patents. The overbasedproducts are preferably prepared from the alkaline earth metal oxides,hydroxides, and alcoholates. The alkaline earth metal lower alkoxidesare the preferred alcoholates.

The promoters, that is, the materials which facilitate the incorporationof the excess metal into the overbased product are also quite diverseand well known in the art as evidenced by the cited patents. Aparticularly comprehensive discussion of suitable promoters is found in2,777,874; 2,695,910; and 2,616,904. These include the alcoholic andphenolic promoters which are preferred. The alcoholic promoters includethe alkanols of one to about twelve carbon atoms such as methanol,ethanol, arnyl alcohol, octanol, isopropanol, and mixtures of these andthe like. Phenolic promoters include a variety of alkylatedhydroxy-substituted benzenes and naphthalenes. A particularly usefulclass of phenols are the monoand dialkylated phenols in which the alkylsubstituent contains from about 6 to about 200 carbon atoms.Illustrative phenolic promoters are the heptylphenols, octylphenols,dodecylphenols, nonylphenols, polypropene (M.W. of l50)-substitutedphenol, polyisobutene (M.W. of 350)-substituted phenols, cyclohexylphenol, 'behenyl phenol. Mixtures of the various promoters are alsouseful. Water is used in combination with the promoters in someinstances to increase their effectiveness.

It should be apparent that the overbased products may retain all or aportion of the promoter. That is, if the promoter is not volatile (e.g.,an alkyl phenol) or otherwise readily removable from the overbasedmaterial, at least some promoter remains in the overbased product. Thepresence or absence of the promoter in the overbased material used toprepare the molybdenum-containing complexes does not represent acritical aspect of the invention. Obviously, it is within the skill ofthe art to select a volatile promoter such as a lower alkanol, e.g.,methanol, ethanol, etc., so that the promoter can be readily removedprior to forming the disperse system or thereafter.

Suitable acidic materials are also disclosed in the above cited patents,for example, 2,616,904. The overbased products used as startingmaterials are preferably prepared using inorganic acidic materials suchas HCl, S0 S0 CO ,H S, N 0 etc. The overbased products prepared with COare particularly suitable although those prepared with SO or 50;; arealso very useful. Materials capable of producing the acidic reactants insitu may also be used. For example, urea, carbamates, and ammoniumcarbonates produce CO in situ.

In preparing the overbased products, the compound to be overbased, asubstantially inert organic solvent therefor, the metal base, thepromoter, and the acidic material are brought together and a chemicalreaction ensues. The exact nature of the resulting overbased product isnot known. However, it can be adequately described for purposes of thepresent specification as a single phase homogeneous solution of a GroupII metal-containing complex formed from the metal base, the acidicmaterial, and the compound being overbased. Since the overbased productsare well-known and as they are used merely as intermediates in thepreparation of the molybdenum-containing additives, the exact nature ofthe products is not criti- 'cal to an understanding of the presentinvention.

The temperature at which the acidic material is contacted with theremainder of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about C. to 300 C., and preferably from about C. to about250 C. When an alcohol or mercaptan is used as the promoting agent, thetemperature usually will not exceed the reflux temperature of thereaction mixture and preferably will not exceed about 100 C.

A typical preparation of an overbased product would involve mixing aphenolic promoter, a Group II metal base, and the organic compound to beoverbased and treating the mixture with carbon dioxide at a temperatureof at least about 50 C., preferably from 80 C. to 250 C. The uppertemperature limit is determined by the decomposition point of thereaction mixture. The car bonation is preferably carried out in thepresence of a fluid diluent, usually an organic solvent in which theorganic compound to be overbased and the product is soluble. Solventscommonly useful for this purpose are substantially inert organicsolvents such as benzene, toluene, chlorobenzene, naphtha, dodecane,xylene, mineral oil, and combinations thereof. For purposes of thisinvention, mineral oil and combinations of at least 50% by Weightmineral oil and one or more other solvents are preferred. The amount andtype of diluent employed should be selected so that the final overbasedproduct comprises from about 10% to about 70% by weight of the solution.

The relative amounts of the compound to be overbased and the metal baseare such that at least 1.1 equivalents of the metal base is used perequivalent of the compound to be overbased. There appears to be no upperlimit on the amount of the metal base which may be used in the process.For practical reasons, however, the amount of the metal base seldomexceeds 25 equivalents per equivalent of the compound being overbased. Agreater amount of the metal compound may be used but there appears to beno particular advantage attending such use. Usually, from about 2 toabout 15 equivalents of the metal base is used.

The equivalent weight of a given organic compound which is to beoverbased depends upon the number of functional groups in the moleculeand the equivalent weight of the metal compound depends upon the valenceof the metal and the number of the metal radicals in the molecule. Thus,the equivalent weight of a phenol is determined by the number of hydroxyradicals attached to the aromatic nucleus; the equivalent Weight of acarboxylic acid ester is determined by the number of ester radicals inthe molecule; the equivalent weight of an alcohol is determined by thenumber of hydroxy radicals in the molecule; the equivalent weight of asulfoxide is determined by the number of sulfoxide radicals in themolecule; the equivalent Weight of an amine is determined by the numberof amino radicals in the molecule; and the equivalent weight of thecondensation product of an amine and a lower aldehyde is determined bythe number of the amino nitrogen radicals in the molecule. For instance,the equivalent weight of sperm oil is its molecular Weight (asdetermined by, e.g., its saponification equivalent); that of oleylalcohol is its molecular weight; that of N-alkyl alkylene diamine isone-half its molecular weight; that of distearyl ester of ethyleneglycol is onehalf its molecular weight; that of heptylphenol is itsmolecular weight; that of 2,2'-didecyl-4,4-methylenebisphenol isone-half its molecular weight; that of didodecyl sulfoxide is itsmolecular Weight; that of the condensation product of N-alkyltetraethylene pentamine and an aldehyde is one-fifth its molecularWeight; that of an alkali metal hydroxide is its molecular Weight; thatof an alkali metal oxide is one-half its molecular weight; and that ofan alkaline earth metal oxide or hydroxide is onehalf its molecularweight.

It will be noted that where the compound to be overbased is a mixture oftwo or more compounds capable of being overbased (e.g., organic acid anda phenol), the relative equivalent amount of the metal base to thismixture has reference to the total number of equivalents in the mixture.To illustrate, Where the ratio of equivalents of the metal base to amixture of compounds to be overbased is 2:1 and the mixture comprises aphenol and another compound capable of being overbased a ratio ofequivalents of 1:4, respectively, the reaction mixture will comprise oneequivalent of a phenol, 4 equivalents of the other compound, andequivalents of a metal base.

When this reaction mixture is contacted with the acidic material, eitherin the presence of or in the absence of a diluent, it is usually aheterogeneous mixture. As acidification (e.g., carbonation) proceeds,the metal base becomes solubilized in the organic phase and thecarbonated product eventually becomes a homogeneous composition which isreadily soluble in hydrocarbon solvents such as benzene, xylene ormineral oil. It is not necessary in most instances that all of the metalbase present in the process mixture should be so converted in order toproduce a soluble homogeneous product. Such a product is often obtained,for example, when as little as 75% of the metal base is carbonated.

The molybdenum-containing anions used in preparing the additives providemolybdenum metal in the final product. Accordingly, the exactcomposition of these anions is not particularly critical to the presentinvention and quite diverse molybdenum-containing anions are suitable.For practical reasons, the molybdenum compound from which the anions arederived should be at least partially soluble in at least one of theother components of the reaction mixture. As the reaction mixtureusually comprises only organic liquids and as most molybdenum-containingcompounds are not soluble in such liquids, a solvent for the molybdenumcompound is usually incorporated into the reaction mixture. Preferably,a solution of molybdenum containing anions is introduced into thereaction mixture. Water is usually employed as the solvent for thispurpose but other liquid such as dioxane, water-dioxane mixtures, andthe like can also be used. After reaction, this additional solventshould be removed unless it is miscible with the lubricant compositionin which the product is to be used.

The preferred molybdenum-containing anions are the molybdate anions,particularly normal molybdate, M00 1 and paramolybdate, MO7O246 due totheir existence in water-soluble compounds. Other polymolybdate anionssuch as octaniolybdate are also useful as would be the thioanalogs ofthese molybdenum-containing anions. Because of their availability andthe excellent results obtained through their use, the commercial sourcesof ammonium molybdates and ammonium paramolybdates are excellent sourcesof molybdenum anions. These commercial products are designated ammoniummolybdate, molybdic acid, and molybdic acid.

In addition to the normal molybdate and polymolybdate anions, theheteropolymolybdate anions can be used in preparing themolybdenum-containing organic complexes. These are themolybdenum-containing anions produced by acidifying solutions ofmolybdate and one or more other oxyanions or metal ions. Arepresentative heteropolymolybdate would correspond to the formula [X MOO Where X corresponds to P Si, Sn, etc.

The cation of the molybdenum-containing compounds which furnish theanions is not particularly critical except to the extent that it maydetermine the degree of solubility of the compound in a given solvent.Because of their water solubility, the ammonium, magnesium, thallous,and alkali metal molybdenum anion-containing salts will normally beused. Of these the alkali metal salts are preferred and the ammoniumsalts are particularly preferred, particularly the commercial sourceswhich are designated by the producers as (NH Mo O and (NH4)2MO207 andthe various hydrates thereof such as (NH4)6'MO7024'4H20, etc.

Various molybdenum-containing compounds and their corresponding anionsare well known in the art. See for example, F. A. Cotton and G.Wilkinson, Advanced Inorganic Chemistry, pages 782-790, IntersciencePublishers, N.Y. 1962.

Having discussed the intermediates from which the molybdenum-containingorganic complexes are prepared, it is now possible to more specificallyidentify the various groups forming the complex. Thus, in the formula RM A E R is an equivalent of the oil-soluble organic compound which isoverbased to produce the overbased starting material, e.g., the group ifasulfonic acid is overbased. The identity of A depends upon the acidicmaterial used in the overbasing process. For example, if carbon dioxideis used as the acidic material, two equivalents of A correspond to thegroup Obviously, the actual identity of E depends on the particularmolybdenum-containing anions used as intermediates in the process. Thus,two equivalents of E could correspond to the group MoO In preparing themolybdenum complexes, the solution of the overbased Group IImetal-containing reactant and the molybdenum-containing anions will bereacted in amounts such that the molar ratio of Group II metal in theoverbased reactant to molybdenum in the molybdenum-containing anion willbe about 1:0.05 to about 1:10 in the reaction mixture. It is notessential that all the molybdenum anion present actually react andbecome a part of the complex but the reaction should continue until atleast a portion of the molybdenum anions react with Group II metal. Themolar ratio of Group II metal to vmolybdenum metal in themolybdenum-containing complex thus produced may vary from about 120.05to about 1:5 and usually from about 1:0.1 to about 1:3.

Complexes wherein the ratio is about 1:02 to about 1:1.7 have been foundto be very useful,

The temperature at which the solution of the overbased product andmolybdenum-containing anions are contacted is not a particularlycritical factor in the process. However, a temperature of at least about20 C. should be employed to avoid an unduly slow reaction and tofacilitate mixing, especially where mineral oil is used as a solvent forthe overbased product. The upper temperature is limited only by thedecomposition temperature of the reactants and the products. However, asthe molybdenum-containing anions are normally employed in aqueoussolutions, it may be desirable not to exceed the boiling point of water(or other molybdenum anion-containing solvent) during the reaction toreduce the water loss. Of course, higher temperatures can be employedconveniently in conjunction with superatmospheric pressure or refluxconditions without water loss. When sufficient molybdenum complex hasbeen formed, water and other low boiling solvents (relative to theboiling point of mineral oil) can be readily removed by increasing thetemperature of the reaction mass and/or lowering the pressure. Reactiontemperatures of about 20 C. to about 150 C. are typical and atemperature of about 40 C. to about 95 C. usually provides very goodresults.

As mentioned supra, the reaction is facilitated if conducted in thepresence of a peptizing agent. Suitable peptizing agents include thewell-known class of diverse materials used as dispersants in variouslubricating oils.

The products which function effectively as dispersants in lubricatingoils and, hence, also function as peptizing agents in preparing themolybdenum'containing complexes, are extremely diverse in nature.Representative peptizing agents and US. patents illustrating them arethe polyglycol substituted polymers disclosed in 2,892,783; polyvinylalcohols partially esterified with one or more carboxylic acids,2,951,050; dibenzoates of polyethylene glycols andalkoxyalkylphthalates, 2,956,870; sulfonates of N-substituted propylenediamines, 2,989,387; copolymers of alkylesters of alpha,beta-unsaturated carboxylic acids, esters of alpha, beta-unsaturatedcarboxylic acids and polyhydroxy alcohols, and, optionally, an alpha,beta-unsaturated monocarboxylic acid, 2,993,032 and 3,001,942; reactionproducts of monoand diamines with the anhydrides of partially esterifiedthiophosphoric acids and a boron acid or anhydride, 3,031,401; sulfonicacid salts of basic nitrogen-containing vinyl polymers, 3,038,- 857;polymers of alkyl esters of alpha,beta-unsaturated carboxylic acids orfatty acid esters of unsaturated alcohols and an imide of maleicanhydride with a polyalkylene polyamine, 3,048,544; the amine additionproducts of oil-soluble sulfonic acid, 3,058,910; graft copolymersderived from free-radical polymerizable monomers containing carbon,hydrogen, and oxygen and nitrogen-containing comonomers, 3,067,163; thereaction products of hydrolyzed phospho-sulfurized hydrocarbons withamines and boron compounds, 3,089,851; copolymers of alkylacrylates andcyanoalkylacrylates, 3,108,- 967; polyamides of aliphatic fatty acidsand polyamines, 3,110,673; amine salts of thiophosphonic acids,3,143,506; unsaturated esters of boron acids, 3,152,166; oil solublecopolymers of N-vinyl pyrrolidones and various other ethylenicallyunsaturated monomers, particularly methacrylic acid esters of highermolecular weight alcohols, e.g., lauryl, cetyl, and stearyl alcohols,British specification 822,620; and the like.

The N-alkyl alkylenediamines and the condensation products thereof withlower aliphatic aldehydes are also suitable peptizing agents. Theseproducts are described in more detail above in regard to the organicmaterials which are suitable for overbasing.

However, the preferred class of peptizing agents is the well-known groupof dispersants derived from substituted succinic acids. These are theesters, acidic esters, half esters-half amides, acidic amides, amides,irnides, amidines, amine salts, and metal salts of substituted succinicacids wherein the substituent contains at least about 50 aliphaticcarbon atoms. The substituent is generally a saturated or unsaturatedaliphatic hydrocarbon group although it may contain pendant aryl groupsor inert polar groups. However, the polar groups should not be presentin sufficiently large numbers to alter the substantially hydrocarboncharacter of the substituent. Exemplary polar groups include halo, keto,ether, aldehyde, nitro, etc. The upper limit on the number of polargroups is about 10% by weight based on the weight of the hydrocarbonportion of the substituent.

The source of the hydrocarbon substituent on the succinic acid moiety ofthe dispersants includes principally the high molecular weightsubstantially saturated petroleum fractions and substantially saturatedolefin polymers, particularly polymers of monoolefins having from 2 to30 carbon atoms. The especially useful polymers are the polymers ofl-mono-olefins such as ethylene, propene, l-butene, isobutene, l-hexene,l-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, and Z-methyl-S-propyl-l-hexene. Polymers of medial olefins, i.e., olefins in whichthe olefinic linkage is not at the terminal posi tion, likewise areuseful. They are illustrated by Z-butene, 3-butene, and 4-octene.

Also useful are the interpolymers of the olefins such as thoseillustrated above with other interpolymerizable olefinic substances suchas aromatic olefins, cyclic olefins, polyolefins. Such interpolymersinclude, for example, those prepared by polymerizing isobutene withstyrene; isobutene with butadiene; propene with isopropene; ethylenewith piperylene; isobutene with chloroprene; isobutene withp-methylstyrene; l-hexene with 1,3-hexadiene; l-octene with l-hexene;l-heptene with l-pentene; 3-methyl-l-butene with l-octene;3,3-dimethyl-l-pentene with l-hexene; isobutene with styrene andpiperylene; etc.

The relative proportions of the mono-olefins to the other monomers inthe interpolymers influence the stability and oil-solubility of thefinal products derived from such interpolymers. Thus, for reasons ofoil-solubility and stability and the interpolymers contemplated for usein this invention should be substantially aliphatic and substantiallysaturated, i.e., they should contain at least about preferably at leastabout 95%, on a weight basis, of units derived from aliphaticmono-olefins and no more than about 5% of olefinic linkages based on thetotal number of carbon-to-carbon covalent linkages in the substituent.Preferably, the percentage of olefinic linkages should be less than 2%of the total number of carbonto-carbon covalent linkages.

Specific examples of such interpolymers include the copolymer of 95% ofisobutene and 5% of styrene; the terpolymer of 98% of isobutene with 1%of piperylene and 1% of chloroprene; the terpolymer of 95% of isobutenewith 2% of l-butene and 3% of l-hexene; the terpolymer of 80% ofisobutene with 10% of I-pentene and 10% of l-octene; the copolymer of80% of l-hexene and 20% of l-heptene; the terpolymer of of isobutenewith 2% of cyclohexene and 8% of propene; and the copolymer of 80% ofethylene and 20% of propene. The percentages refer to the percent byweight of total interpolymer weight.

Another source of hydrocarbon substituents are saturated aliphatichydrocarbons, e.g., highly refined molecular weight white oils orsynthetic alkanes such as are obtained by hydrogenation of the highmolecular weight olefin polymers illustrated above or other highmolecular weight olefinic substances.

Olefin polymers having molecular Weights from about 750 to about 10,000are the preferred source of the substituent with those having molecularweights of about 750 to 5000 being especially preferred. Highermolecular weight olefin polymers having molecular weights of from about10,000 to about 100,000 or more can be used alone or in combination withthe lower molecular weight polymers to prepare the substituted succinicacid reactants. Higher molecular weight substituents can impartviscosity index improving properties to the final product of thisinvention.

The substituted succinic acids are readily available from the reactionof maleic anhydride with a suitable olefin, olefin polymer, chlorinatedhydrocarbon, and the like as described hereinabove. The reactioninvolves merely heating the two reactants at a temperature of about 100to 200 C. The product of such a reaction is a succinic anhydride havinga large hydrocarbon substituent. The hydrocarbon substituent may containolefinic linkages which may be converted, if desired, to saturated,paraflinic linkages by hydrogenation. The anhydride may be hydrolyzed bytreatment with water or steam to the corresponding acid. It will benoted in this regard that the anhydride is equivalent to the acidinsofar as its utility in the preparation of the dispersants of thisinvention. In fact, the anhydride is often more reactive than the acidand is often preferred.

In lieu of the olefins or chlorinated hydrocarbons, other hydrocarbonscontaining an activating polar substituent, i.e., a substituent which iscapable of activating the hydrocarbon molecule in respect to reactionwith maleic acid or maleic anhydride, may be used in theabove-illustrated reaction for preparing the substituted succinic acids.Such polar substituents are examplified by sulfide, disulfide, nitro,mercaptan, halo, ketoner, or aldehyde radicals. Examples of suchpolar-substituted hydrocarbons include polypropene sulfide,di-polyisobutene disulfide, nitrated mineral oil, di-polyethylenesulfide, brominated polyethylene, etc. Another useful method forpreparing succinic acids and anhydrides involves the reaction ofitaconic acid with a high molecular weight olefin or a polar-substitutedhydrocarbon at a temperature usually within the range of from about100-200 C.

The dispersants prepared from the reaction of polyolefin-substitutedsuccinic acid or anhydride and monoor poly-amines, particularlypolyalkylene polyamines having up to about amino nitrogens, areespecially suitable dispersants. The reaction products generallycomprise a mixture of amides, imides, amine salts, amidines, etc. Thereaction products of polyisobutene-substituted succinic anhydride andpolyethylene polyamines containing up to about 10 amino nitrogens areexcellent peptizing agents. The substituted succinic acid oranhydride-amine products are disclosed in 3,018,250; 3,024,195;3,172,892; 3,216,936; 3,219,666; and 3,272,746. Included within thisgroup of dispersants are those products prepared by posttreating thereaction product of the amine and substituted succinic anhydride withcarbon disulfide, a boron compound, an alkyl nitrile, urea, thiourea,guanidine, alkylene oxide, and the like as disclosed in 3,200,107;3,256,185; 3,087,936; 3,254,025; 3,281,428; 3,278,550; 3,312,619; andBritish specification 1,053,577.

The metal salts of the foregoing substituted succinic acids aredisclosed in US. Pat. 3,271,310. The metal moiety of the salt ispreferably a Group I or II metal, aluminum, lead, tin, cobalt, nickel,or zinc.

The esters of the above substituted succinic acid are also very usefulpeptizing agents. These esters are prepared by reacting acid oranhydride with a monoor polyhydric alcohol or phenol according tostandard procedures for preparing esters of carboxylic acids. Typicalesters of this type are disclosed in British specification 981,850, US.Pat. 3,311,558, and copending application Ser. No. 567,052 filed July22, 1966. The preferred esters are the esters of thepolyolefin-substituted succinic acids or anhydrides in polyhydricaliphatic alcohols containing 2 to 10 hydroxy groups and up to about 40aliphatic carbon atoms. Such alcohols include ethylene glycol, glycerol,sorbitol, pentaerythritol, polyethylene glycol, diethanol amine,triethanolamine, N,N-di(hydroxyethyl)-eth ylene diamine, and the like.If the alcohol reactant contains reactive amino hydrogens (or if anamine reactant contains reactive hydroxyl groups), it is obvious that amixture comprising the reaction products of the substituted succinicacid reactant and both the hydroxyl and amino functional groups ispossible. Such reaction products can include half-ester, half-amides,imides, and the like. See 3,342,033.

The peptizing agent can be incorporated into the reaction mixture in anamount of about 1% to about 50% by weight based on the Weight of thesolution of overbased reactant employed. Normally, from about 3% toabout 20% by Weight of the peptizing agent will be employed. Since thepresence of these peptizing agents is beneficial in the final products,i.e., the lubricating compositions, the peptizing agent in no Wayinterferes with the use of the molybdenum-containing complexes inlubricating compositions.

The following examples demonstrate typical preparations of the overbasedcompounds which are useful as intermediates in preparing molybdenumcomplexes.

EXAMPLE 1 A mixture of 630 grams (2 equivalents) of a rosin amine(consisting essentially of dehydroabietyl amine) having a nitrogencontent of 44% and 245 grams (1.2 equivalents) of heptylphenol having ahydroxyl content of 8.3% is heated to C. and then mixed with 230 grams(3 equivalents) of barium oxide at 90-140 C. The mixture is purged withnitrogen at 140 C. A portion, 600 grams, of the mixture is diluted with400 grams of mineral oil and filtered. The filtrate is blown with carbondioxide, diluted with benzene, heated at the reflux temperature, heatedto remove benzene, mixed with xylene and filtered. The filtrate, a 20%xylene solution of the product, has a barium sulfate ash content of25.1%, a nitrogen content of 2%, and a reflux base number of 119. Thereflux base number refers to the basicity of the product expressed interms of milligrams of KOH equivalent to one gram of the composition.

EXAMPLE 2 (a) An amine-aldehyde condensation product is obtained asfollows: Formaldehyde (420 grams, 14 moles) is added in small incrementsto a mixture of N-octadecyl propylenediamine (1392 grams, 4 moles),mineral oil (3000 grams), water (200 grams) and calcium hydroxide (42grams, condensation catalyst) at the reflux temperature, l05 C. The rateof addition of formaldehyde is such as to avoid excessive foaming. Themixture is heated at reflux temperature for one hour, then slowly heatedto 155 C., and blown with nitrogen at 150l55 C. for two hours to removeall volatile components. It is then filtered. The filtrate, 93% of thetheoretical yield, is a 65.4% oil solution of the aminealdehydecondensation product having a nitrogen content of 2.4%. A portion (1850grams, 3.2 equivalents of nitrogen) is mixed with heptylphenol (185grams, 0.97 equivalent), mineral oil (1485 grams) and 90% pure bariumoxide (1060 grams, 12.6 equivalents) and heated to 70 C. Water (500grams) is added throughout a onehour period while maintaining thetemperature at 70- 100 C. The mixture is heated at =-115 C. for 4.75hours and then heated to 150 C. Thereafter it is carbonated at 150 C.and filtered. The filtrate is 57.8% oil solution of the basic metalcomposition having a nitrogen content of 0.87% and a barium sulfate ashcontent of 29.5%.

(b) A product similar to that of (a) but with a lower mineral oilcontent is made by mixing 1000 parts (by weight) of N-octadecylpropylenediamine, 490 parts of mineral oil, 32 parts calcium oxide, and143 parts water at about 44 C. and slowly heated to about 102 C. underreflux conditions over a one-hour period. While maintaining the mixtureat l00105 C., 303 parts of paraformaldehyde are added over three hours.Mixing is continued 13 for another hour under the same conditions andthen the mass is heated to about 150 C. over two and one-half hours. Twohundred seventy eight parts of distillate were removed and the residuefiltered.

In a separate reaction vessel, a mixture of 197 parts (by weight)mineral oil and 119 parts of heptylphenol is heated to 93-99" C. Whilemaintaining this temperature, 465 parts of barium hydroxide monohydrateis added over a four-hour period. The temperature is then raised toabout 150 C. and 149 parts of the above amineformaldehyde product isintroduced over a one-half hour period. Carbon dioxide is introducedinto the mixture via submerged line at 15 parts per hour for 7 hoursduring which the temperature is maintained at about 150 C. An additional100 parts of mineral oil is added and this reaction mixture is blownwith nitrogen for two hours during which the temperature is regulated atabout 150 C. This reduces the water content of the mixture to about0.3%. Forty parts of a commercial filter aid is added and the mixturefiltered. The filtrate is an oil solution of barium overbasedamine-formaldehyde condensate containing about 36% by weight mineral oiland having a barium content of 30.8%.

EXAMPLE 3 A mixture of 423 grams (1 equivalent) of sperm oil, 123 grams(0.602 equivalent) of heptylphenol, 1214 grams of mineral oil and 452grams of water is treated at 70 C. with 612 grams (8 equivalents) ofbarium oxide. The mixture is stirred at the reflux temperature for onehour and then heated to 150 C. while carbon dioxide is bubbled into themixture beneath its surface. The carbonated product is filtered and thefiltrate has a sulfate ash content of 35%.

EXAMPLE 4 A partially acylated polyamine reactant is prepared asfollows. A mixture (565 parts by weight) of an alkylene amine mixtureconsisting of triethylene tetramine and diethylenetriamine in weightratio of 3:1 is added at 20- 80 C. to a mixture of equivalent amounts ofa naphthenic acid having an acid number of 180 (1270 parts) and oleicacid (1110 parts). The total quantity of the two acids is such as toprovide one equivalent for each two equivalents of the amine mixture.The reaction is exothermic. The mixture is blown with nitrogen while itis being heated to 240 C. over 4.5 hours and thereafter heated at thistemperature for 2 hours. Water is collected as the distillate. To theabove residue ethylene oxide (140 parts) is added at l70l80 C. over atwo-hour period while nitrogen is bubbled through the reaction mixture.The reaction mixture is then blown with nitrogen for 15 minutes anddiluted with 940 parts of xylene to a solution containing 25% of xylene.The resulting solution has a nitrogen content of 5.4% and a base numberof 82 at pH of 4, the latter being indicative of free amino groups. Aportion of the above xylene solution (789 grams, 3 equivalents ofnitrogen) is heated to 150 C./2 mm. Hg to distill oif xylene and is thenmixed with heptylphenol (having a hydroxyl content of 8.3%; 367 grams,1.8 equivalents). To this mixture there is added 345 grams (4.5equivalents) of barium oxide in small increments at 90111 C. The mixtureis heated at 90-120 C. for 2.5 hours and blown with carbon dioxide for1.75 hours. It is diluted with 130 grams of xylene, heated at 150 C. for3.5 hours, and then diluted with an additional 20% of its weight ofxylene and filtered. The filtrate has a barium sulfate ash content of33.2%, a nitrogen content of 3.52%, and a reflux base number of 134.

EXAMPLE 5 A sulfoxide is prepared by treating a polyisobutylene of 750average molecular weight with 47.5 percent of its weight of SOC1 for 4.5hours at 200220 C. A mixture of 787 grams (1.0 equivalent) of thissulfoxide, 124

grams (0.6 equivalent) of diisobutyl phenol, 550 grams of mineral oiland 200 grams of water is heated to 70 C. and then treated with 306grams (4.0 equivalents) of barium oxide. This mixture is heated atreflux temperature for one hour and then treated at C. with carbondioxide until the mixture is substantially neutral. The resultingmixture is filtered to yield a clear oil-soluble liquid having a bariumsulfate ash content of 22.8%.

EXAMPLE 6 To a mixture of 268 grams (1.0 equivalent) of oleyl alcohol,675 grams of mineral oil, 124 grams (0.6 equivalent) of diisobutylphenol, and 146 grams of water, at 70 C. there is added 308 grams (4.0equivalents) of barium oxide. This mixture is heated at refluxtemperature for one hour, then at 150 C. while a stream of carbondioxide is bubbled through the mixture until it is substantiallyneutral. The thus acidified mixture is filtered and the clear brownoil-soluble filtrate found to have a barium sulfate ash content of29.8%.

EXAMPLE 7 To a mixture of 500 grams (1.0 equivalent ofpolyisobutylphenoxy-ethanol, 124 grams (0.6 equivalent) of heptylphenol, 848 grams of mineral oil and grams of water there is added at 70C., 306 grams (4.0 equivalents) of barium oxide. This mixture is heatedat reflux temperature for an hour at 150 C. while bubbling carbondioxide beneath the surface for three hours. The carbonated mixture isfiltered to yield a liquid product having a barium sulfate ash contentof 23.8%.

EXAMPLE 8 To a mixture of 174 grams (1. 0 equivalent) of N-octadecylp-ropylenediarnine, 124 grams (0.6 equivalent) of diisobutylphenol, 766grams of mineral oil, and 146 grams of water there is added 306 grams(4.0 equivalents) of barium oxide and the whole is refluxed for an hour.Water is removed by raising the temperature to 150 C. whereupon carbondioxide is bubbled through the mixture at this temperature until it issubstantially neutral. The mixture is filtered to yield a clearoil-soluble liquid having a barium sulfate ash content of 28.9%.

EXAMPLE 10 To a mixture of 516 grams (2.0 equivalents) of an N-octadecylpropylene diamine-ethylene oxide condensation product, 1776 grams ofmineral oil and 360 grams of water there is added 756 grams (9.9equivalents) of barium oxide. After refluxing this mixture for one hourthe temperature is raised to 150 C. and carbon dioxide is bubbledthrough the mixture until it is substantially neutral. Filtration yieldsa liquid product having a barium sulfate ash content of 29.6%.

EXAMPLE 11 To a mixture of 408 grams (2 equivalents) of heptylphenolhaving a hydroxy content of 8.3% and 264 grams of xylene, there is added383 grams (5 equivalents) of barium oxide in small increments at 85-100"C. and 6 grams of water. The resulting mixture is carbonated at 100-130C. and then filtered. The filtrate is heated to 100 C. and subsequentlydiluted with xylene to a 25 xylene solution. This solution is found tohave a barium 15 sulfate ash content of 41% and a reflux base number of137.

EXAMPLE 12 A 65.4% oil solution of the amine aldehyde condensationproduct of Example 2(a) (1400 grams, 2.4 equivalents), heptylphenol (140grams, 0.73 equivalent), and barium oxide (368 grams, 4.78 equivalents)is heated to 70 C. and 250 grams of water added over a one-hour periodwhile maintaining a temperature of 70-100 C. The mixture is heated atthe reflux temperature of 110- 115 C. for four hours and then at 150155C. for 0.5 hour. It is then blown with carbon dioxide at 140150 C. andfiltered. The filtrate is a 47% oil solution of the desired product andhas a sulfate ash content of 27.8%, a nitrogen content of 1.65%, and areflux base number of 78.

EXAMPLE 13 The procedure of Example 12 is repeated except that theamount of barium oxide used is 1091 grams (14.2 equivalents) and thatmineral oil, 1041 grams, is added to the reaction mixture beforecarbonation. The product is a 50% oil solution and has a barium sulfateash content of 36.1%, a nitrogen content of 0.83%, and a reflux basenumber of 168.

EXAMPLE 14 A mixture of polyisobutene (molecular Weight of 300)-substituted phenol having a hydroxy content of 3.76% (200 grams, 0.44equivalent) and heptylphenol having a hydroxy content of 8.3% (200grams, 0.98 equivalent), and xylene (200 grams) is heated to 80 C.whereupon barium oxide (218 grams, 2.84 equivalents) is added to themixture in small increments at 80104 C. Thereafter, grams of water isadded and the resulting mixture is carbonated and nitrogen blown at 148C. for 2.3 hours. After filtering, the filtrate is heated to 165 12 mm.Hg and the residue is diluted with xylene solution. The xylene solutionis found to have a barium sulfate ash content of 36.7% and a reflux basenumber of 171.

EXAMPLE 15 A mixture of 65.4% mineral oil solution of the aminealdehydecondensation product of Example 2 (1400 grams, 2.4 equivalents),heptylphenol (281 grams, 1.46 equivalents), mineral oil (1636 grams),barium oxide (893 grams, 11.6 equivalents) is heated to 70 C. Water (500grams) is added in one hour at 70-110 C. The mixture is heated at refluxtemperature (110115 C.) for 4 hours, dried by heating it to 150 C. andthen at 145 -1'50 C. for 0.5 hour. It is blown with carbon dioxide at145 l50 C. until it is substantially neutral to phenolphthalein and thenfiltered. The filtrate is a 58% oil solution of the product and has abarium sulfate ash content of 27.3% and a reflux base number of 126.

EXAMPLE 16 A mixture of 520 parts (by weight) of a mineral oil, 480parts of a sodium petroleum sulfonate (molecular Weight of 480), and 84parts of water is heated at 100 C. for 4 hours. The mixture is thenheated with 86 parts of a 76% aqueous solution of calcium chloride and72 parts of lime (90% purity) at 100 C. for 2 hours, dehydrated byheating to a water content of less than 0.5%, cooled to 50 C., mixedwith 130 parts of methyl alcohol, and then blown with carbon dioxide at50 C. until substantially neutral. The mixture is then heated to 150 C.to distill off methyl alcohol and water and the resulting oil solutionof the basic calcium sulfonate filtered. The filtrate is found to have acalcium sulfate ash content of 16% and a metal ratio of 2.5. A mixtureof 1305 grams of the above carbonated calcium sulfonate, 930 grams ofmineral oil, 220 grams of methyl alcohol, 72 grams of isobutyl alcohol,and 38 grams of amyl alcohol is prepared, heated to C., and subjected tothe following operating cycle four times: mixing with 143 grams ofcalcium hydroxide and treating the mixture with carbon dioxide until ithas a 'base number of 32-39. The resulting produce is then heated to 155C. during a period of 9 hours to remove the alcohols and then filterdthrough a siliceous filter-aid at this temperature. The filtrate has acalcium sulfate ash content of 39.5%, and a metal ratio of 12.2.

EXAMPLE 17 A basic metal salt is prepared by the procedure described inExample 16 except that the slightly basic calcium sulfonate having ametal ratio of 2.5 is replaced with a mixture of that calcium sulfonate(280 parts by weight) and tall oil acids (970 parts by weight, having anequivalent weight of 340) and that the total amount of calcium hydroxideused is 930 parts by weight. The resulting highly basic metal salt ofthe process has a calcium sulfate ash content of 48%, a metal ratio of7.7, and an oil content of 31%.

EXAMPLE 18 A highly basic metal salt is prepared by the procedure ofExample 17 except that the slightly basic calcium sulfonate startingmaterial having a metal ratio of 2.5 is replaced with tall oil acids(1250 parts by weight, having an equivalent Weight of 340) and the totalamount of calcium hydroxide used is 772 parts by weight. The resultinghighly basic metal salt has a metal ratio of 5.2, a calcium sulfate ashcontent of 41%, and an oil content of 33%.

The following examples illustrate specific embodiments of the presentinvention.

EXAMPLE I An aqueous mixture of ammonium paramolybdate tetrahydrate,(NH4)6M07024'4H20, is prepared by mixing 411 grams thereof with 300grams of water and maintaining the temperature of the mixture at about60 C. Four -gram portions of this mixture are added to 457 grams of thebarium overbased amine aldehyde condensate of Example 2(b) over a 3.5hour period while maintaining the temperature of the reaction mass atabout 95 C. This results in a molar ratio of barium to molybdenum of3:1. During the addition of the aqueous mixture, ammonia and carbondioxide are evolved. Thereafter, the reaction mass is dried by heatingto C. while blowing with nitrogen and filtered yielding 550 grams of anoil solution of the desired molybdenum-containing complex. Analysis ofthe product establishes that about 65% of the molybdenum employed in thereaction is retained in the molybdenum-containing complex thus produced.

EXAMPLE II (A) A mixture of 44 parts (all parts refer to parts byweight) of the product of Example 2(b), 10 parts mineral oil, and 24parts of the reaction product of polyisobutene (molecular weight750)-substituted succinic anhydride with a commercial mixture ofpolyethylene polyamines having an average composition corresponding tothat of tetraethylene pentamine (reacted in a ratio of equivalents of1:1 according to the procedure of US. patent 3,172,892, e.g., Example 12thereof) is prepared and heated to about 75 C. over a 1.5 hour period.The weight ratio of peptizing agent to overbased material is 5:95. Tothis solution there is added 520 parts of an aqueous ammonium molybdatesolution previously prepared by mixing 265 parts by weight of water and265 parts by weight of a commercial ammonium molybdate (ammoniumdimolybdate sold by the Climax Molybdenum Company having a compositioncorresponding to the formula (NHQ Mo o containing about 56.5% by weightmolybdenum) over a 1.5 hour period while maintaining a temperature atabout 7080 C. resulting in a molar ratio of barium to molybdenum of1:153. The resulting reaction mass is heated under reflux conditions atabout 150 C. for about 8.8 hours. Subsequently, the mixture is blownwith nitrogen at about parts per hour while maintaining the temperatureat about 150 C. for an additional 1.3 hours. The nitrogen blowing isthereafter ceased, the mixture is maintained at about 150 C. for anadditional hour and the entire reaction mass is filtered. The filtratecontains the desired molybdenum-containing complex and is characterizedby having 19.67% by weight molybdenum and 21.81% by weight barium.

(B) To a mixture of 2,285 grams of the overbased product of Example 2(b)and 125 grams of the peptizing agent referred to in II(A) above, thereis added slowly over three hours 2600 grams of an aqueous solution ofammonium paramolybdate tetrahydrate (prepared by mixing 1300 grams ofthe molybdate and 1300 grams of water) while maintaining a temperatureslightly above 70 C. The weight ratio of peptizing agent to overbasedproduct is 5:95 and the barium to molybdenum molar ratio of 121.47.Ammonia, carbon dioxide, and water are evolved during the ensuingreaction. Thereafter, nitrogen is bubbled through the reaction mass toremove water and gases during which time the product is heated to 170for four hours. Then a commercial filter aid is added and the mass isfiltered. The filtrate weighs 2,710 grams and contains 20.2% by weightmolybdenum, 21.6% by weight barium, and 25.3% by weight oil.

(C) The procedure of II(B) is repeated except that the weight ratio ofpeptizing agent to the product of 2(b) is 25:75 and 457 grams of theproduct of 2(b) are reacted with 354 grams of the molybdate solutiongiving a molar ratio of bariumzmolybdenum in the reaction mass of 111.After filtration, 500 grams of filtrate containing the desiredmolybdenum-containing complex are obtained. The filtrate comprises 23.4%by weight mineral oil, 13.3% by weight molybdenum, and 19.3% by weightbarium.

(D) To a mixture of 24 grams of water, 457 grams of the product of 2(b),and 25 grams of the peptizing agent of II(A) preheated to 90 C., thereis added 102 grams of the commercial ammonium molybdate powder describedin Example II(A). The mixture is maintained at this temperature forseveral hours with constant agitation of the mass. After drying at 170C. and filtering, a filtrate is obtained weighing 485 grams andcomprising 9.4% by weight molybdenum. The barium to molyb denum molarratio in the reaction mass is 120.6 and the weight ratio of peptizingagent to overbased product is 5:95.

(E) The procedure of (D) is followed with the exception that 51 grams ofthe ammonium molybdate of Example II(A) is utilized. Thus the reactionmixture contains a molar ratio of bairum to molybdenum of 1:0.3. Thefiltrate contains 26.4% by weight barium and 5.5% by weight molybdenum.

EXAMPLE III (A) A mixture of 1000 parts by weight of polyisobutenehaving a molecular weight of about 1000 and 90 parts by weight ofphosphorus pentasulfide is heated to about 260 C. over five hours andthereafter maintained at that temperature for an additional five hoursin an atmosphere of nitrogen. The reaction mass is then cooled to 150 C.and blown with steam for 5 hours. The resultingphosphosulfurized-hydrolyzed material has a phosphorus content of 2.35%by weight and a sulfur content of 2.75% by weight.

A suspension of 311 parts by weight of barium hydroxide in 485 parts ofmineral oil is heated to 140-150 C. and 300 parts of thephosphosulfurized-hydrolyzed product prepared above is added over aone-hour period. To the resulting mixture there is added over a one-halfhour period 153 parts of heptylphenol. The resulting mixture is thenblown with carbon dioxide for 2.3 hours while maintaining a temperatureof 150-155 C. Subsequently, 181 parts of barium hydroxide are added tothe mass over a 30-minute period and the carbonation is resumed. Anadditional 181 parts of barium hydroxide is added at the end of 2 hoursand carbonation is continued for an additional two and one-half hours.Thereafter, 274 parts of mineral oil are added and the resultingsolution is dried by blowing nitrogen therethrough while maintaining thetemperature of the mass at 150 C. After filtration, mineral oil is addedto dilute the solution to a barium sulfate ash concentrate of 38.5%. Theproduct thus obtained is a phosphorus content of 0.35%, a sulfur contentof 0.38%, a reflux base number of 168, and a metal ratio of 14.2.

A mixture of 1226 grams of the product produced above and 1226 grams ofthe peptizing agent described in II(A) is formed and heated to about C.To this mixture there is added an aqueous ammonium paramolybdatesolution (prepared by mixing 353 grams of the ammonium paramolybdatetetrahydrate of Example I and 353 grams of water). The molybdatesolution is added over about a 40-minute period. The resulting mixtureis maintained at about C. for 4 hours. Thereafter, the reaction mixtureis heated to about 170 C. for 3 hours and filtered. The filtrate weighs2,416 grams and comprises 42.1% by weight mineral oil, 10.4% by weightbarium, 6.39% by weight molybdenum, and 0.17% by weight phosphorus.

(B) A substituted succinic acid ester of pentaerythritol is prepared byreacting polyisobutenyl (molecular weight about 750)-substitutedsuccinic anhydride and pentaerythritol in a molar ratio of 1:1 at atemperature of about 190-200 C. while blowing the reaction mass withnitrogen gas at the rate of about 10 parts by weight per hour. Threehundred forty-two parts by weight mineral oil is used as the reactionmedium. Thereafter, an additional 113 parts by weight of mineral oil isadded and the entire mass is filtered. The ester contained in thefiltrate is an excellent peptizing agent.

Following the procedure of III(A), 1839 grams of thephosphosulfurized-hydrolyzed product of (A), 460 grams of theoil-solution of the substituted succinic acid ester of pentaerythritolas produced above, and 1058 grams of an ammonium molybdate solution(produced by mixing 529 grams of ammonium paramolybdate tetrahydrate and529 grams of water) are reacted. The reaction mixture thus producedcontains a weight ratio of peptizing agent to overbased material of20:80 and a molar ratio of barium to molybdenum of 1:1. Afterfiltration, 1448 grams of an oil solution of the desiredmolybdenumcontaining complex is obtained as the filtrate. The filtratecontains 4.8% by weight barium and 3.19% by weight molybdenum.

EXAMPLE IV (A) To a mixture of 1820 grams of the product of Example 2(b)and 96 grams of the peptizing agent described in Example III(B), thereis added 2120 grams of ammonium molybdate solution prepared by mixing1060 grams each of water and ammonium parabolybdate tetrahydrate. Themolybdate solution is added over a one-hour period while maintaining thetemperature at about 7585 C. Thereafter, the reaction mixture is driedby heating to about 170 C. while blowing with nitrogen for 3.5 hours toremove water, ammonia, and carbon dioxide. The reaction product isfiltered at a temperature of 150 C. The filtrate contains 21.53% byweight barium and 20.5% by weight molybdenum. The ratio of peptizingagent to overbased material in the reaction mixture is 5 and the molarratio of barium to molybdenum is 1:1.5.

(B) A peptizing agent is prepared according to U.S. patent 3,200,107(e.g., Example 9 thereof, etc.) by reacting polyisobutene(molecularweight 1000)-substituted succinic anhydride (1.5 equivalents) with about3 equivalents of a commercial mixture of polyethylene polyamines havingan average composition of tetraethylene pentamine by heating the mixtureto about C. over a 6-hour period and thereafter blowing it with nitrogenfor an additional 5 hours. Thereafter, 1.5 equivalents of carbondisulfide is added over a one-hour period while 19 maintaining thetemperature in the range of about 140- 150 C. The resulting mixture isheated an additional hour and then blown with nitrogen for 3 hours andfiltered. (See Example 9 of 3,200,107.)

To a reaction mixture of 1820 grams of the product of Example 2(b) and320 grams of a 40% by weight oil solution of the above describedpeptizing agent there is added 708 grams of ammonium paramolybdatetetrahydrate dissolved in an equal amount of water while maintaining atemperature of about 82 C. This temperature is maintained for abouthours. Subsequently, the reaction mixture is heated to about 107 C.,nitrogen gas is bubbled through the reaction mixture. Thereafter themixture is filtered. The filtrate contains 21.5% barium and 15.35%molybdenum. The Weight ratio of peptizing agent to overbased organiccompound in the reaction mixture is :85 and the molar ratio of barium tomolybdenum is 1:1.

(C) A peptizing agent is prepared as in Example II(A) with the exceptionthat 2 equivalents of the amine mixture are reacted with each equivalentof the substituted succinic acid anhydride.

Following the procedure of Example 1V(A), 1820 grams of the product ofExample 2(b), 96 grams of a 41% oil solution of the above describedpeptizing agent, and 2120 grams of an aqueous solution of ammoniummolybdate (prepared by mixing 1060 grams each of ammonium paramolybdatetetrahydrate and water) are reacted to produce a molybdenum-containingcomplex. The resulting filtrate contains 21.08% barium and 20.99%molybdenum. The Weight ratio of peptizing agent to overbased organicstarting material is 5:95 and the molar ratio of barium to molybdenum is121.5.

EXAMPLE V An amine aldehyde condensation product is prepared accordingto Example 2(b) by reacting a mineral oil solution of N-octadecylpropylene diamine with formaldehyde in the presence of calcium hydroxideas the condensation catalyst. The resulting amine-formaldehydecondensation product is an effective peptizing agent.

A mixture comprising 674 grams of a calcium overbased petrosulfonic acidhaving a metal ratio of 12.2 and 225 grams of the oil solution of theamine-aldehyde condensation product identified above is heated to about100 C. Thereafter, an ammonium molybdate solution (prepared bydissolving 354 grams of ammonium paramolybdate tetrahydrate in 354 gramsof water) is added to the mixture over a period of one hour whilemaintaining the reaction mixture at between 80 and 95 C. This reactionmixture is characterized by a ratio of peptizing agent to overbasedpetrosulfonate of 25:75 and a molar ratio of calcium to molybdenum of1:1. The reaction mixture was maintained at a temperature of about 95 C.for about four hours and thereafter heated slowly to 170 C. whilebubbling nitrogen through the reaction mass. These conditions weremaintained for about four hours and the reaction mass subsequentlyfiltered. The oil solution of the molybdenum-containing complexes thusproduced is characterized by a calcium content of 2.47% by weight and amolybdenum content of 5. 81% by weight.

EXAMPLE VI A mixture of 1371 grams of the product of 2(b) and 344 gramsof the peptizing agent of Example II(A) is warmed to 65 C., producing aWeight ratio of peptizing agent to overbased material of :80. To thismixture there is added 730 grams of powdered sodium molybdate dihydrate(Na MoO '2H O) and 347 grams of water resulting in a molar ratio ofbarium to molybdenum of 1:1. This mixture is held at 100110 C. for 8.5hours, subsequently dried under a vacuum at 150 C., and filtered. Thefiltrate contains 23.3% by weight barium and 1.0% by weight molybdenum.

The foregoing examples demonstrate one of the reasons that ammoniummolybdates are particularly useful in preparing themolybdenum-containing complexes, particularly where the overbasedmaterial is a carbonated product. During the reaction between theoverbased starting material and the molybdenum-containing anions,carbonate is displaced by the molybdenum-containing anions and ammoniaand carbon dioxide are evolved. The evolution of these byproducts asgases facilitates the preparation of the desired complexes. If thecation of the molybdenum-containing reactant is one which forms anoilinsoluble product, a haze or precipitate can form which should befiltered from the reaction product. As noted above, the peptizing agentsassist in minimizing or eliminating hazes, etc.

It will be understood that the above examples are merely illustrative ofthe preparation of the molybdenum-containing complexes used as additivesin the compositions of the present invention. By applying the abovetechniques to other overbased materials and/or othermolybdenumcontaining reactants as described hereinbefore, a wide varietyof molybdenum-containing complexes can be prepared.

The molybdenum-containing complexes of the invention can be employed inlubricating oils and greases in various amounts to improve the extremepressure an anti-wear properties of the lubricants. Usually, they willbe employed in amounts such that the molybdenum will comprise from about0.001% to about 15% by weight of the final lubricating composition.Preferably, however, the molybdenum-containing additives of theinvention are utilized in amounts that will produce a molybdenum contentof about 0.05% to about 5% by Weight in the final lubricatingcomposition. Due to the basic metal content of the complexes, it shouldbe obvious to those skilled in the art that the complexes also functionas detergents in lubricating oils in the same manner as the overbasedintermediates from which they are prepared.

It has been determined that the extreme pressure capabilities andanti-wear properties of the present molybdenum-containing complexes areespecially effective in combination with one or more known, conventional-E.P. or anti-wear additives such as chlorinated paraffin wax,benzylpolysulfides, alkylpolysulfides, sulfur chloridetreated olefins,sulfur chloride-treated fatty oils, sulfurized sperm oil, sulfurizedmineral oils, sulfurized fatty oils, zinc diorganodithiophosphates, leadnaphthenates, zinc or lead dialkyldithiocarbonates, etc. Theseconventional additives are generally characterized by one or moresulfur, halogen, phosphorus, carboxyl, or carboxylate salt substituentsand are well known to those skilled in the art as amply illustrated byC. V. Smalheer and R. K. Smith, Lubricant Additives, (particularly pages-911) published by The Lezius-Hiles Co., Cleveland (1967), and C. W.Georgi, Motor Oils And Engine Lubrication, (particularly pages 209-217),published by Reinhold Publishing Corp., New York (1950), and thereferences cited therein. In many instances, these combinations appearto co-act synergistically.

The molybdenum-containing complexes of this invention will ordinarily beused in combination with other lubricant additives usually found inlubricating oils and greases. Such additives include, for example,detergents of the ash-containing type, ashless detergents ordispersants, viscosity index improving agents, pour point depressants,rust inhibiting agents, anti-foam agents, and oxidation and corrosioninhibitors and the like.These other additives are discussed in detail inthe patents and publications discussed above.

The ash-containing detergents are exemplified by oilsoluble neutral andbasic salts of alkali or alkaline earth metal with sulfonic acids,carboxylic acids or organic phosphorus acids characterized by at leastone direct carbon-to-phosphorus linkage (such as those prepared by thetreatment of an olefin polymer, e.g., polyisobutene having a molecularweight of 1000, with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride). The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontium,and barium. The basic salts of such compounds are those wherein thenumber of equivalents of metal is present in a stoichiometrically largeramount than the number of equivalents of organic radicals. The commonlyemployed methods for preparing the basic salts involves heating amineral oil solution of an acid with a stoichiometric excess of a metalneutralizing agent such as the metal oxide, hydroxide, carbonate,bicarbonate, or sulfide at a temperature above 50 C. and filtering theresulting mass as explained hereinbefore With regard to the preparationof the overbased materials suitable for preparing themolybdenum-containing complexes.

The ashless detergents useful in lubricating oil compositions have beendescribed in detail hereinbefore in regard to the peptizing agentsuseful in preparing the molybdenum-containing complexes.

Examples of oxidation-inhibitors, corrosion-inhibitors, and otherextreme pressure agents include benzyldisulfidebis-(chlorobenzyl)disulfide, dibutyltetrasulfide, sulfurized methylester of oleic acid, sulfurized alkylphenol, sulfurized dipentene,sulfurized terpene, sulfurized Diels- Alder adducts such as the adductof butadiene and butylacrylate, phosphosulfurized hydrocarbons such asthe reaction product of a phosphorus sulfide with terpentine ormethyloleate, phosphorus esters including principally dihydrocarbon andtrihydrocarbon phosphites such as dibutylphosphite, diheptylphosphite,dicyclohexylphosphite, pentylphenylphosphite, diphentylphenylphosphite,tridecylphosphite, distearylphosphite, dimethylnaphthylphosphite,polypropylene(molecular weight 500)-substituted phenylphosphite,diisobutyl-substituted phenylphosphite, metal thiocarbonates such aszinc dioctyl-dithiocarbonates and barium heptylphenyl dithiocarbonate,Group II metal phosphorodithioates such as zincdicyclohexylphosphorodithioates, zinc dioctylphosphorodithioate, bariumdi (heptylphenyl)-phosphorodidthioate, cadmium,dinonylphosphorodithioate, zinc salts of phosphorodithioic acidsproduced by the reaction of phosphorus pentasulfide with an equimolarmixture of isopropyl alcohol and n-hexyl alcohol, and the leadphosphorodithioate salts corresponding to the foregoing metalphosphorodithioates.

As is Well known, the amount of each additive to be employed in a givencomposition can vary Widely. Thus, depending on the particular use ofthe lubricating composition and the type of additive underconsideration, the additives Will be employed in amounts ranging fromabout 0.001% to about 20% by weight of the lubricating composition.Thus, in an internal combustion engine crankcase lubricating oil, theamount of detergent and/r dispersant may vary from about 0.1% to aboutby weight. The conventional E.P. agents and anti-wear additives(oiliness, lubricity, and film strength additives as they are sometimescalled) can be employed in amounts of from about 0.01% to about 10% ormore by Weight depending on the nature of the additive and theenvironment in which the lubricant must function.

An illustrative lubricating composition for use in the crankcase of aninternal combustion engine would be an SAE mineral lubricating oilcontaining 2% (by Weight) of a dispersant produced by reacting apolyisobutenyl (M.W.750)-substituted succinic anhydride with apolyethylene polyamine mixture in an equivalent ratio of anhydride toamine of 1:1, 0.07% of phosphorus as zinc dioctylphosphorodithioate, 2%of a barium detergent pre pared by neutralizing the hydrolyzed productof phosr phosulfurized polypropylene, 3% of a carbonated, bariumoverbased mahogany acid (metal ratio, 6), 3% of the copolymer ofdecyl-methacrylate and diethylaminoethylacrylate reacted in a weightratio of 95:5, 2% of the product of Example II(a), 1% of sulfurizedsperm oil, 0.03% of an anti-foam agent, 0.02% of a pour pointdepressant, and 3% of a viscosity index improver. Another example is anSAE mineral oil composition containing 3% by Weight of the samesubstituted succinic anhydride-polyethylene polyamine reaction product,0.1% phosphorus as zinc di-(isobutylphenyl)phosphorodithioate, 10% ofchlorinated pariffin Wax having a chlorine content of (by weight), 2% ofdibutyltetrasulfide, 2% of sulfurized dipentene, and 1.5% of the productof Example II(b). Other compositions are readily available by adding themolybdenum-complexes to presently available lubricating oils and greaseor substituting the complexes for all or part of the BF. and anti-Wearadditives which may be present in such compositions.

While the foregoing generally describes the use of the additives interms of improving mineral lubricating oils and mineral oil basedlubricating greases, it should be understood that the present inventionis not limited to such mineral oil based lubricating compositions. Otherlubricating oils, natural as well as synthetic, can be used as the baseof the lubricating oil and grease compositions contemplated by thepresent invention. Such natural and synthetic bases include hydrocarbonoils derived from polymerization of olefins and synthetic oils producedfrom alkylene oxides such as polyethylene oxide and polypropylene oxidepolymers or the esters and ethers thereof. The synthetic ester oils suchas those produced from polycarboxylic acids and alcohols, includingglycols and polyglycols, are also contemplated as being within the scopeof the present invention. Exemplary of these oils are dibutyl adipate,di-(2-ethylhexyl)-sebacate, dilauryl azelate, etc.

The effectiveness of the molybdenum-containing complexes of theinvention is demonstrated by the results obtained when compositionscontaining varying amounts of the products are subjected to Timken OKLoad test. Data compiled from such tests are tabulated hereinbelow. Allpercentages given in the table refer to percent by Weight of a totalcomposition.

IABLE I Molybdenum complex Commer- Timkeu Lubri- Lubricial E.P. PreparedBazMo molar OK load eating eating addiaccording ratio in test oil greasetive to Example Amount, reaction results, percent percent percent No.percent mixture pounds 3 II(a) 1 1:1. 47 :65 3 II(a) 2 1:1. 47 :75 3 I1.42 1:1.2 65:65 3 I 2. 84 1:1. 2 75:85 3 II(a) 1 1:1.47 65:65 3 II(a) 21:1.47 :80

1 Commercial S.A.E. mineral lubricating oil.

Commereial lithium-base grease.

Commercial E.P. agent in form of oil solution of (a) lead and (b) zinesalts of diorgano phosphoroditlnolc acids and (c) the reaction productof a 2:1 molar ratio isobutene and sulfur monochloride (S 012).

From Table I, it is readily seen that by increasing the amount of themolybdenum-containing complex as indicated, the load-carrying or extremepressure capability of compositions A and C are increased over whilethese capabilities of the grease composition of E are increased overThese composiitons also demonstrate that the molybdenum-containingcomplexes function effectively in combination with other E.P. agentsboth in greases and lubricating oils.

Similarly, by employing standard engine tests, e.g., the 1964 OldsmobileValve Tip Wear Test, it has been established that themolybdenum-containing complexes reduce the wear (valve tip scuff, etc.)in operating internal combustion engines when employed as lubricatingoil additives in amounts usual for such additives, e.g., about 2% byweight. There is, obviously, a relationship between the ability of anadditive to increase the load-carrying properties of a metal and theability to reduce Wear, i.e. lessen friction.

Many other obvious variations of this invention will be apparent tothose skilled in the art. These variations, insofar as covered by theappended claims, are within the contemplated scope of the invention.

What is claimed is:

1. A lubricating composition comprising a major proportion of alubricating oil and minor proportion of an oilsoluble,molybdenum-containing composition sufficient to improve the extremepressure properties of said lubricating composition, saidmolybdenum-containing composition having been produced by contacting (1)a solution of an oil-soluble, carbonated, basic Group IImetal-containing organic complex of a condensation product ofN-alkyl-substituted alkylene polyamine containing 8 to 40 carbon atomsin the N-alkyl groups with a lower aliphatic aldehyde containing lessthan 6 carbon atoms, said complex being characterized by a metal ratioof at least 2, with (2) molybdenum-containing anions derived fromammonium, magnesium, thallous, and alkali metal molybdates at atemperature of at least 20 C. for a period of time suflicient for atleast a portion of the molybdenum-containing anions to react with theGroup II metal of said complex and to release carbonate from saidcomplex, the molar ratio of Group II metal to molybdenum being fromabout 120.05 to 1:5.

2. A lubricating composition according to claim 1 wherein themolybdenum-containing anions are present as aqueous solutions ofammonium molybdate of ammonium paramolybdate and the Group II metal isan alkaline earth metal.

3. A lubricating composition according to claim 2 wherein theN-alkyl-substituted alkylene polyamine has from about 12 to about 30carbon atoms in the N-alkyl groups and the molar ratio of alkaline earthmetal to molybdenum is about 1:0.1 to about 1:3.

4. A lubricating composition according to claim 2 wherein theN-alkyl-substituted alkylene polyamine is an N-alkyl-alkylenediaminehaving from about 10 to about 30 carbon atoms in the alkyl radical and 2to 4 carbon atoms in the alkylene radical.

5. A lubricating composition according to claim 4 wherein the molarratio of alkaline earth metal to molybdenum is from about 120.1 to about1:3.

6. A lubricating composition according to claim 5 wherein the aldehydeis formaldehyde, paraformaldehyde, aqueous formalein, acetaldehyde,propionaldehyde, or butylaldehyde.

7. A lubricating composition according to claim 6 wherein the molarratio of alkaline earth metal to molybdenum is about 1:02 to about1:1.7.

8. A lubricating composition according to claim 2 wherein saidcondensation product is produced by the process comprising carbonating amixture comprising (A) mineral oil,

(B) one equivalent of a phenolic composition consisting of a mixture ofalkylated phenol having from about 6 to about 200 aliphatic carbon atomsand an oil-soluble condensation product of formaldehyde and anN-alkyl-alkylenediamine having from about 12 to about 30 carbon atoms inthe alkyl radical and from 2 to 4 carbon atoms in the alkylene radicalwherein the ratio of equivalents of the alkylated phenol to thecondensation product is within the range of from about 0.1:1 to 10:1;and

(C) from about 2 to about 15 equivalents of barium hydroxide.

9. A lubricating composition according to claim 6 wherein themolybdenum-containing composition is prepared by contacting a mineraloil solution of a carbonated, basic, barium-containing organic complexwith an aqueous solution of molybdate or paramolybdate anions at atemperature within the range of about 20 C. to about C. for a period oftime sufiicient for at least a portion of the carbonate to be displaced,and subse quently removing substantially all water from the reactionmixture, said organic complex being the product produced by carbonatinga mixture comprising (A) mineral oil,

(B) one equivalent of a phenolic composition consisting essentially of amixture of 1) a promoter selected from the class consisting of monoanddialkylated phenols having 6 to about 200 aliphatic carbon atoms and (2)the condensation product of about 3 moles of formaldehyde and about onemole of N-dodecyl trimethylenediamine, wherein the ratio of equivalentsof the heptylphenol to the condensation product is within the range offrom about 0.5:1 to about 5:1; and

(C) from about 2 to about 10 equivalents of barium hydroxide.

10. A lubricating composition according to claim 9 wherein the aqueoussolution containing molybdate anions is an aqueous solution of ammoniummolybdate.

11. A lubricating composition according to claim 10 wherein the aqueoussolution of molybdate anions is an aqueous solution of ammoniumparamolybdate.

12. A lubricating composition according to claim 11 wherein the promoteris selected from the class consisting of heptylphenols, octylphenols,and nonylphenols.

13. A lubricating composition according to claim 1 wherein molybdateions are contacted with the organic complex in the presence of apeptizing agent selected from the class consisting of oil-solubleesters, amides, imides, amidines, amine salts, and metal salts ofsubstituted succinic acids wherein the substituents contain at leastabout 50 aliphatic carbon atoms.

14. A lubricating composition according to claim 13 wherein the succinicacids are polyolefin-substituted succinic acids.

15. A lubricating composition according to claim 1 wherein molybdateanions are contacted with the organic complex in the presence of apeptizing agent selected from the class consisting of (a)N-alkylalkylenediamines wherein the alkyl group contains from about 12to about 30 carbon atoms and the alkylene groups contain from 2 to 4carbon atoms and (b) the oil-soluble condensation products of saidN-alkylalkylenediamines with formaldehyde, with the proviso that whenthe carbonated, basic, Group II metal-containing organic complex is acomplex of an lN-al kylalkylenediamine or condensation product thereofwith formaldehyde, the peptizing agent is an excess of (a) or (b) overthat required to form said comp ex.

References Cited UNITED STATES PATENTS 2,795,550 6/1957 Harle et al.25249.7 2,795,552 6/1957 Abbott et a1. 25249.7 3,047,500 7/ 1 962 Matson25242.7 3,050,538 8/1962 Hugel et al. 25242.7 X 3,184,410 5/1965Bretherick 25242.7

(Other references on following page) UNITED 25 26 STATES PATENTS PATRICKP. GARVIN, Primary Examiner yphers et a1. 25249.7 X W. H. CANNON,Assistant Examiner Elliott et a1 252-49.7 X Farmer et a1. 25242.7 X US.Cl. X.R. Price 25233 5 Dorer 25218 X 251 18, 25, 33.4, 34.7, 37.2, 40.7,42.7, 46.4

